WO2019112293A1 - Composition de plastifiant et composition de résine la comprenant - Google Patents

Composition de plastifiant et composition de résine la comprenant Download PDF

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WO2019112293A1
WO2019112293A1 PCT/KR2018/015248 KR2018015248W WO2019112293A1 WO 2019112293 A1 WO2019112293 A1 WO 2019112293A1 KR 2018015248 W KR2018015248 W KR 2018015248W WO 2019112293 A1 WO2019112293 A1 WO 2019112293A1
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terephthalate
triethylene glycol
weight
ethylhexyl
based material
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PCT/KR2018/015248
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English (en)
Korean (ko)
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김현규
정석호
조윤기
문정주
김주호
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주식회사 엘지화학
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Priority to MX2020002959A priority Critical patent/MX2020002959A/es
Priority to BR112020006374-6A priority patent/BR112020006374B1/pt
Priority to EP18885459.0A priority patent/EP3663344A4/fr
Priority to JP2020513875A priority patent/JP6972484B2/ja
Priority to CN201880044696.4A priority patent/CN110832019B/zh
Priority to US16/625,229 priority patent/US10851220B2/en
Publication of WO2019112293A1 publication Critical patent/WO2019112293A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the present invention relates to a plasticizer composition and a resin composition containing the same.
  • the plasticizer reacts with the polycarboxylic acid, such as phthalic acid and adipic acid, to form the corresponding ester.
  • the polycarboxylic acid such as phthalic acid and adipic acid
  • plasticizers are added with various additives such as fillers, stabilizers, pigments, anti-fogging agents, and resins such as polyvinyl chloride (PVC) to give various processing properties, and they are processed by extrusion molding, injection molding, calendering, , Pipes, flooring, wallpaper, sheets, artificial leather, tarpaulins, tapes and food packaging.
  • additives such as fillers, stabilizers, pigments, anti-fogging agents, and resins such as polyvinyl chloride (PVC) to give various processing properties, and they are processed by extrusion molding, injection molding, calendering, , Pipes, flooring, wallpaper, sheets, artificial leather, tarpaulins, tapes and food packaging.
  • PVC polyvinyl chloride
  • a plasticizer composition which can maintain excellent mechanical properties such as tensile strength, elongation and modulus, is excellent in transmittance and transparency, and has improved plasticization efficiency, and a resin Composition.
  • a terephthalate-based material comprising dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate and di (2-ethylhexyl) terephthalate; And a triethylene glycol diester material comprising triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate. / RTI >
  • a resin composition comprising 100 parts by weight of a resin; And 5 to 150 parts by weight of the plasticizer composition described above.
  • the plasticizer composition according to an embodiment of the present invention can be used in a resin composition and can be maintained at a level of excellent mechanical properties such as tensile strength, elongation and modulus, excellent in transmittance and transparency, Can be provided.
  • butyl may mean n-butyl, which is generally referred to, and may also mean “isobutyl”, and hence the term butyl is not limited to n-butyl can be used to refer to both n-butyl and isobutyl.
  • a mixed plasticizer composition comprising three kinds of terephthalate-based materials and three kinds of triethylene glycol diester-based materials.
  • the terephthalate-based material is dibutyl terephthalate, (3-ethylhexyl) terephthalate and di (2-ethylhexyl) terephthalate, wherein the triethylene glycol diester material is selected from the group consisting of triethylene glycol bis (2-ethylhexanoate), 2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate.
  • the three kinds of terephthalate-based materials are excellent in transparency and transparency, are excellent in mechanical properties and are advantageous in application to products in contact with foods or in contact with human bodies. However, they are disadvantageous in that they are relatively inferior in plasticizing efficiency, And a process step has been added to the process to increase the product unit price.
  • the triethylene glycol diester substance is a typical eco-friendly substance and is excellent in terms of plasticization efficiency.
  • it has poor transparency and transparency, and thus has a disadvantage in application to a product contacting with food or a product contacted with human body , And the mechanical properties are considerably low.
  • the plasticizer composition according to one embodiment of the present invention is a plasticizer composition capable of solving the above problems and can be greatly improved in plasticization efficiency by mixing with a material having no environmental issues such as triethylene glycol diester- It can be solved by keeping the physical properties, transparency and transparency at the same level or more.
  • the weight ratio of the terephthalate-based material and the triethylene glycol diester-based material contained in the plasticizer composition may be 90:10 to 10:90, and the upper limit may be 90:10, 85:15, 80:20, 70:30, or 60:40, and the lower limit may be 10:90, 15:85, 20:80, 30:70, or 40:60.
  • the specific properties can be maintained at the level of excellent properties possessed by the respective compounds, and the specific properties can be further improved.
  • the terephthalate-based material is a substance in which a disester group is bonded to the para position of the benzene ring.
  • a 2-ethylhexyl group and a butyl group are bonded, and two butyl groups, 2-ethylhexyl group, And a compound in which two 2-ethylhexyl groups are combined.
  • the composition of the three compounds is preferably 0.5 to 50% by weight of dibutyl terephthalate; 3.0 to 70% by weight of butyl (2-ethylhexyl) terephthalate; And di (2-ethylhexyl) terephthalate in an amount of 0.5 to 85% by weight, and the weight ratio can be controlled by controlling the amount of the feedstock during the reaction. Further, it may be formed in an amount of 0.5 wt% to 50 wt%, 10 wt% to 50 wt%, and 35 wt% to 80 wt%, more preferably.
  • the triethylene glycol diester-based material may be a mixture of three kinds of compounds represented by the following formula (a).
  • Ra and Rb each independently represent , or to be.
  • the triethylene glycol diester-based material may be a mixture of triethylene glycol, benzoic acid, and 2-ethylhexanoic acid, which are produced by the esterification reaction, and Ra and Rb are each a benzoic acid-derived hydrocarbon group or Ethyl hexanoic acid, and the three compounds are those in which Ra and Rb are both benzoic acid-derived hydrocarbon groups, Ra and Rb are both 2-ethylhexanoic acid-derived hydrocarbon groups, and Ra and Rb are 2-ethylhexane An acid-derived hydrocarbon group and a benzoic acid-derived hydrocarbon group.
  • the three compounds included in the triethylene glycol diester-based material may be represented by the following formulas A-1 to A-3.
  • composition of the three compounds of the triethylene glycol diester-based material is preferably 0.5 to 85% by weight of triethylene glycol bis (2-ethylhexanoate); 3.0 to 70% by weight of (2-ethylhexanoyloxy) triethylene glycol benzoate; And 0.5 to 50% by weight of triethylene glycol dibenzoate. Furthermore, it is more preferably 20% by weight to 70% by weight, 20% by weight to 70% by weight, and 1% by weight to 40% by weight.
  • the excellent physical properties It is possible to obtain an effect of improving the plasticization efficiency while being able to be taken, and if the mixing weight ratio is adjusted at the same ratio as described above, the property improving effect can be optimized.
  • a plasticizer composition according to another embodiment of the present invention is a plasticizer composition containing dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, di (2-ethylhexyl) terephthalate and terephthalate represented by the following formula Terephthalate-based materials; And a triethylene glycol diester material comprising triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate, Di (2-ethylhexyl) terephthalate and terephthalate represented by the following formula (1) are not less than 99.0 parts by weight, and terephthalate represented by the following formula (1) Is less than 1.0 part by weight.
  • R < 1 &gt is a straight chain or branched alkyl group having 1 to 13 carbon atoms and is not a 2-ethylhexyl group.
  • (2-ethylhexyl) terephthalate and 99.5 parts by weight or more of di (2-ethylhexyl) terephthalate and terephthalate represented by the following formula (1) May be less than 1.0 part by weight, preferably 99.2 parts by weight or more and less than 0.8 parts by weight, more preferably 99.5 parts by weight or less and 0.5 parts by weight or less, optimally 99.9 parts by weight or less and 0.1 parts by weight or less, Parts by weight and less than 0.05 parts by weight.
  • the plasticizer composition may be prepared by blending a terephthalate-based material and a triethylene glycol-diester-based material, and then mixing the plasticizer composition to prepare a plasticizer composition. have.
  • the terephthalate-based material may be prepared by a direct esterification reaction of terephthalic acid and a secondary alcohol, or a transesterification reaction of di (2-ethylhexyl) terephthalate and butyl alcohol.
  • the alcohol may be 2-ethylhexyl alcohol and butanol, and the mixed alcohol thereof may be directly applied to the esterification reaction.
  • the direct esterification reaction may be performed by adding terephthalic acid to an alcohol, adding a catalyst, and reacting in a nitrogen atmosphere; Removing unreacted alcohol and neutralizing the unreacted acid; And dehydration and filtration by vacuum distillation.
  • the alcohol may be used in an amount of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of terephthalic acid.
  • the catalyst for the esterification examples include acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkylsulfuric acid, aluminum sulfate, lithium fluoride, potassium chloride , A metal oxide such as cesium chloride, calcium chloride, iron chloride and aluminum phosphate, a metal oxide such as heteropoly acid, a natural / synthetic zeolite, a cation and an anion exchange resin, an organic metal such as tetra alkyl titanate and a polymer thereof It can be more than a species.
  • the catalyst may use tetraalkyl titanate.
  • the amount of the catalyst to be used may vary depending on the type of catalyst. For example, in the case of a homogeneous catalyst, 0.01 to 5 wt%, 0.01 to 3 wt%, 1 to 5 wt%, or 2 to 4 wt% And in the case of a heterogeneous catalyst, it may be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of reactants.
  • the reaction temperature may be in the range of 180 to 280 ° C, 200 to 250 ° C, or 210 to 230 ° C.
  • the transesterification reaction may be performed to produce the terephthalate-based material.
  • di (2-ethylhexyl) terephthalate may react with butyl alcohol.
  • trans-esterification reaction used in the present invention means a reaction in which an alcohol and an ester react with each other as shown in Reaction Scheme 1 below to mutually exchange R "of an ester with R ' :
  • ester compositions when the trans-esterification reaction is carried out, when the alcohol alkoxide attacks the carbon of the two ester (RCOOR ") group present in the ester compound, When attacking carbon of RCOOR group; In the case where the reaction is unreacted and unreacted, three kinds of ester compositions can be produced by number in three cases.
  • the trans-esterification reaction is advantageous in that it does not cause wastewater problems as compared with the acid-alcohol interesterification reaction, and can proceed under no-catalyst, thereby solving the problems in using the acid catalyst.
  • composition ratio of the terephthalate-based material produced through the transesterification reaction as described above is as described above, and the composition ratio of the mixture can be controlled according to the addition amount of the alcohol.
  • the amount of the alcohol to be added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, more specifically 5 to 40 parts by weight, based on 100 parts by weight of the terephthalate compound.
  • the greater the amount of alcohol added the larger the mole fraction of the terephthalate compound involved in the trans-esterification reaction, so that the content of the two terephthalate compounds as the product in the mixture may increase, The content of the terephthalate compound present unreacted may correspondingly decrease.
  • the molar ratio of the reactant terephthalate to alcohol is, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, There is an effect of obtaining an ester plasticizer composition having an excellent effect.
  • the composition ratio may be a mixing composition ratio generated by the esterification reaction, may be an intended composition ratio by further mixing specific compounds, and the mixing composition ratio may be appropriately adjusted to meet desired properties,
  • the composition ratio of the mixture of the three kinds of terephthalate-based materials is not limited to the above-mentioned range, and any one of the three types of terephthalate may be further added to change the composition ratio thereof. .
  • the transesterification reaction is carried out at a reaction temperature of 120 to 190 ° C, preferably 135 to 180 ° C, more preferably 141 to 179 ° C for 10 minutes to 10 hours, preferably 30 Min to 8 hours, more preferably 1 to 6 hours.
  • the mixture which is a terephthalate-based material having a desired composition ratio within the above temperature and time range can be effectively obtained.
  • the reaction time can be calculated from the point at which the temperature of the reactant is raised to the reaction temperature.
  • the transesterification reaction can be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
  • the acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid
  • the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst or a metal itself.
  • the metal component may be, for example, any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more thereof.
  • the direct esterification reaction and the transesterification reaction can also be used to prepare the triethylene glycol diester-based material described above. That is, conditions such as specific reaction conditions and molar ratios may be similar.
  • triethylene glycol diester-based materials it can be generally prepared by trans esterification reaction, and it can be prepared by using benzoic acid, 2-ethylhexanoic acid, and triethylene glycol as raw materials, and the terephthalate- There may be a difference in using diacids instead of dicarboxylic acids.
  • the method for producing the triethylene glycol diester-based material is not particularly limited, and there is no particular limitation on the production method as long as it is a method capable of providing a mixture of three types of triethylene glycol diesters.
  • the terephthalate-based material and the triethylene glycol diester-based material thus prepared can be blended through a common method, and there is no particular limitation on the blending method.
  • the plasticizer composition comprises 100 parts by weight of a resin such as ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane or thermoplastic elastomer, 5 to 150 parts by weight, 10 to 100 parts by weight, or 30 to 60 parts by weight, based on the weight of the composition, and 70 to 130 parts by weight may be applied depending on the application.
  • a resin such as ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane or thermoplastic elastomer
  • the resin composition may be processed by various methods such as plastisol processing, extrusion or injection molding, calendering, and the like.
  • the resin composition may be applied to wire, automobile interior material, film, sheet, tube, wallpaper, toy, floor material, Can be applied.
  • the resin composition may also include those designed for use in the medical or food industry, such as blood bags, intravenous bags, saline bags, syringes, intravenous syringes, nasogastric tubes, catheter tubes, drainage tubes, Gloves, oxygen masks, corrective maintenance devices, artificial skin, and food packaging materials (e.g., packaging for various beverages, meats and frozen vegetables).
  • those designed for use in the medical or food industry such as blood bags, intravenous bags, saline bags, syringes, intravenous syringes, nasogastric tubes, catheter tubes, drainage tubes, Gloves, oxygen masks, corrective maintenance devices, artificial skin, and food packaging materials (e.g., packaging for various beverages, meats and frozen vegetables).
  • a resin for eco-friendly food packaging materials or a medical resin can be evaluated satisfactorily in the evaluation of the functionality such as transparency and color, and is excellent in adhesion, Basic mechanical properties such as efficiency and heat loss can also exhibit properties equal to or higher than those of conventional plasticizers.
  • the resin composition may further contain stabilizers, anti-fogging agents and the like, and other additives may be further added.
  • the reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol, and finally a mixed composition was prepared.
  • a reactor equipped with a stirrer, a condenser and a decanter was charged with 450.5 g of triethylene glycol, 778.7 g of 2-ethylhexanoic acid, 293.0 g of benzoic acid and 2.0 g of tetranormalbutyl titanate as a catalyst, The esterification reaction was carried out for a period of time.
  • the mixture was subjected to a purification process to obtain 42.4 wt%, 45.4 wt% and 12.2 wt% of triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate, By weight based on the total weight of the composition.
  • plasticizer compositions of the examples were prepared by mixing the materials prepared in Preparation Examples 1 and 2, and are summarized in Table 1 below. Physical properties of the plasticizer compositions were evaluated according to the following test items.
  • the shore (shore A and D) hardness at 25 ° C, 3T 10s was measured using ASTM D2240.
  • a cross head speed was pulled at 100 mm / min (0.25 T) using a UTM (manufacturer; Instron, Model 4466, manufactured by ASTM D638 method) Respectively.
  • the tensile strength was measured in the TD and MD directions and was calculated as follows:
  • Tensile strength (kgf / mm 2) load value (kgf) / thickness (mm) x width (mm)
  • the crosshead speed was pulled at 100 mm / min (0.25 T) using the UTM according to the ASTM D638 method, and then the point at which the specimen was cut was measured.
  • the TD and MD directions were measured , The elongation was calculated as follows, and the higher the item is evaluated as superior:
  • Elongation (%) [length after elongation / initial length] x 100
  • a specimen (1T) with a thickness of 2 mm or more was obtained according to KSM-3156.
  • PS plates were attached to both sides of the specimen and a load of 1 kgf / cm 2 was applied.
  • the specimens were left in a hot air circulating oven (80 ° C) for 72 hours, taken out and cooled at room temperature for 4 hours. After removing the PS attached to both sides of the specimen, we measured the weight loss before and after leaving the oven. The loss was calculated by the following formula.
  • Transition loss (%) [(initial weight of specimen at normal temperature - weight of specimen after leaving oven) / initial weight of specimen at room temperature] x 100
  • the specimens were weighed at 80 ° C for 72 hours, and the specimens were weighed as follows.
  • Heat loss (%) [(Initial specimen weight - Specimen weight after work) / Initial specimen weight] x 100
  • the haze and transparency were measured using an NDH 7000 Haze Meter. The haze was evaluated as being better as the haze was lower and higher as the transparency was higher.
  • the degree of excellent adhesion was evaluated as 5 and 5, respectively.
  • the degree of adhesion was evaluated as 5 and 5, respectively.
  • Specimens were prepared using the mixed plasticizer compositions of the examples and comparative examples described in Table 1 above.
  • PVC polyvinyl chloride resin
  • ESO epoxidized soybean oil
  • LTX-630P LTX-630P
  • anti-fogging agent Almax-9280 were added as stabilizers and mixed at 700 rpm at 98 ⁇ ⁇ .
  • the specimens were prepared by using a roll mill at 160 ° C for 4 minutes and working at 180 ° C for 2.5 minutes (low pressure) and 2 minutes (high pressure) using a press.
  • test pieces were evaluated for each of the test pieces, and the results are shown in Table 2 below.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Hardness Shorea 81.5 81.3 81.1 80.6 80.3 83.0 80.3 Shore D 36.2 36.2 36.1 36.1 36.0 37.3 36.0 Tensile strength (kg / cm 2 ) TD 211.5 210.3 208.9 206.8 207.0 210.0 198.2 MD 230.1 223.8 222.7 226.8 227.7 228.7 210.5 Elongation (%) TD 295.0 292.4 293.0 294.5 291.2 293.2 280.4 MD 292.1 290.3 287.9 284.6 285.9 294.0 267.4 100% modulus TD 92.0 91.7 91.7 91.3 91.3 91.3 94.0 91.0 MD 98.8 98.8 98.5 98.5 98.5 101.1 94.9 Performance loss (%) 1.37 1.35 1.42 1.43 1.48 1.33 1.78 Heat loss (%) 1.88 2.10 2.14 2.38 2.64 1.90 3.71 Haze (%) 3.21 3.20 3.26 3.44 3.58 3.18 5.21 Transparency (%) 91.0 90.2
  • triethylene glycol diester-based material mixed with a terephthalate-based material is superior in tensile strength and elongation to triethylene glycol diester-based material when terephthalate- It can also be seen that, despite the mixing, the figure can be further improved.
  • the physical properties of the respective materials are not equal to or more than those of the respective properties, rather than the linear changes of the physical properties, and the physical properties are improved .
  • the plasticizer composition according to the present invention can provide a resin having excellent plasticization efficiency, improved mechanical properties, and excellent in heat loss, transition loss, haze, and transmittance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de plastifiant et une composition de résine la comprenant. La composition de plastifiant comprend : un matériau à base de téréphtalate comprenant du téréphtalate de dibutyle, du téréphtalate de butyle(2-éthylhexyle) et du téréphtalate de di(2-éthylhexyle) ; et un matériau à base de diester de triéthylène glycol comprenant du triéthylène glycol bis(2-éthylhexanoate), du benzoate de (2-éthylhexanoyloxy)triéthylène glycol, et du dibenzoate de triéthylène glycol. La composition de plastifiant peut conserver d'excellentes propriétés mécaniques telles que la résistance à la traction, l'allongement et le module, et peut avoir une excellente transmittance et une excellente transparence, ainsi qu'une excellente efficacité de plastification.
PCT/KR2018/015248 2017-12-04 2018-12-04 Composition de plastifiant et composition de résine la comprenant WO2019112293A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MX2020002959A MX2020002959A (es) 2017-12-04 2018-12-04 Composicion plastificante y composicion de resina que incluye la misma.
BR112020006374-6A BR112020006374B1 (pt) 2017-12-04 2018-12-04 Composição plastificante e composição de resina que compreende a mesma
EP18885459.0A EP3663344A4 (fr) 2017-12-04 2018-12-04 Composition de plastifiant et composition de résine la comprenant
JP2020513875A JP6972484B2 (ja) 2017-12-04 2018-12-04 可塑剤組成物及びこれを含む樹脂組成物
CN201880044696.4A CN110832019B (zh) 2017-12-04 2018-12-04 增塑剂组合物和包含该增塑剂组合物的树脂组合物
US16/625,229 US10851220B2 (en) 2017-12-04 2018-12-04 Plasticizer composition and resin composition including the same

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KR10-2017-0165272 2017-12-04
KR1020170165272A KR102236923B1 (ko) 2017-12-04 2017-12-04 가소제 조성물 및 이를 포함하는 수지 조성물

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CN (1) CN110832019B (fr)
MX (1) MX2020002959A (fr)
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CN112011125B (zh) * 2020-09-07 2022-11-11 石家庄海关技术中心 一种具有增塑剂迁移值的聚丙烯膜标准样品及其制备方法

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MX2020002959A (es) 2020-08-20
EP3663344A1 (fr) 2020-06-10
US20200190282A1 (en) 2020-06-18
CN110832019A (zh) 2020-02-21
TWI758569B (zh) 2022-03-21
BR112020006374A2 (pt) 2020-09-24
JP2020533448A (ja) 2020-11-19
KR20190065772A (ko) 2019-06-12
JP6972484B2 (ja) 2021-11-24
TW201936871A (zh) 2019-09-16
EP3663344A4 (fr) 2020-08-12
US10851220B2 (en) 2020-12-01
KR102236923B1 (ko) 2021-04-07
CN110832019B (zh) 2021-07-23

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